The present invention relates to a new class of pendant graft copolymers made from a backbone containing allylic groups and specific heterocyclic monomers.
Considering the graft copolymers, U.S. Pat. No. 3,281,310 to Danielson merely relates to the improved adhesion of rubber articles to textiles through the incorporation of the rubber compound of an Ingredient A which may include oxazine or oxazoline among other compounds with an Ingredient B which may be resorcinol or other meta-disubstituted benzene compounds. Only very small amounts of any oxazine compound is added and the improved adhesion occurs through the reaction of the Ingredient A with polar groups such as those contained in the Ingredient B-type compound. Moreover, nowhere is there even suggested the existence of an initial backbone containing allylic chloride groups.
In an article published in the magazine MACROMOLECULES, Volume 6, No. 6, November-December, 1973, Pages 805-808, Saegusa describes the preparation of an ABA-type block copolymer prepared from 2-oxazoline and hydroxyl terminated polybutadiene. However, the polybutadiene backbone completely lacks any initial allylic chloride groups and the route of preparation is through tosylation of the hydroxyl terminated polybutadiene end groups utilizing tosyl chloride. Polymerization is then conducted primarily in a solvent of toluene and DMF with the insoluble block copolymer precipitating out.
In another article by Saegusa appearing in MACROMOLECULES, Volumn 8, No. 4, July-August, 1975, Pages 390-395, a graft copolymer is prepared. However, the graft contains a polystyrene backbone with, of course, the styrene groups being pendant from the ethylene-type backbone. Some of the pendant styrene groups contain chloromethyl groups thereon. Monomers of 2-methyl-2-oxazoline are utilized and form pendant polymers by reaction with the chloromethylated groups on the polystyrene. Cross-linked as well as noncross-linked macroporous bead polymers are formed. The graft copolymer, of course, does not contain any initial allylic chloride groups in the backbone, does not contain any unsaturation in the backbone, and utilizes potassium iodide as a coinitiator in lieu of applicants' various metal salts. Moreover, applicants' pendant polymers are connected directly to the backbone and not to any pendant benzyl groups.
U.S. Pat. No. 4,001,147 to Chamberlain et al, relates to the graft copolymers obtained by reacting oxazoline or oxazine with a cross-linked vinyl aromatic polymer bearing pendant halomethyl groups on the aromatic rings. Macroporous beads prepared in such a manner are particularly useful in removing phenolics from aqueous waste streams and the like. These graft copolymers are similar to Saegusa in that they have merely an ethylene-type backbone, completely lack any initial backbone sites of allylic chloride, and formation of the pendant graft polymers is off of the pendant benzyl groups.
U.S. Pat. No. 4,011,376 to Tomalia describes the preparation of olefin terminated oxazoline homopolymers through the use of allyl chloride or preferably vinyl benzyl chloride and optionally, with sodium iodide as a coinitiator. No teaching or suggestion of the formation of a copolymer is mentioned. Additionally, any further polymerization would require further reaction through the olefin (vinyl) unit to form a copolymer. The Tomalia invention does not utilize allyl chlorinated polymers as initiators for copolymerization or Group 1b salts (e.g. AgSo.sub.3 CF.sub.3) as coinitiators. Hence, it is not pertinent.